U.S. patent number 3,968,148 [Application Number 05/180,142] was granted by the patent office on 1976-07-06 for copolymers of 1-alkenes and acrylic acid derivatives.
This patent grant is currently assigned to Rohm and Haas Company. Invention is credited to Norman A. Leister, Richard J. Piccolini.
United States Patent |
3,968,148 |
Leister , et al. |
July 6, 1976 |
Copolymers of 1-alkenes and acrylic acid derivatives
Abstract
This invention relates to novel oligomers of 1-alkenes and
derivatives of acrylic acids, to methods of making the oligomers,
and to compositions which comprise the oligomers.
Inventors: |
Leister; Norman A. (Huntingdon
Valley, PA), Piccolini; Richard J. (Newtown, PA) |
Assignee: |
Rohm and Haas Company
(Philadelphia, PA)
|
Family
ID: |
22659361 |
Appl.
No.: |
05/180,142 |
Filed: |
September 13, 1971 |
Current U.S.
Class: |
560/205; 554/223;
548/348.1; 548/540; 548/551; 548/312.7; 548/524; 548/550; 548/573;
560/222; 508/472 |
Current CPC
Class: |
C07D
233/16 (20130101); C07D 265/32 (20130101); C08F
220/1812 (20200201); C08F 220/1818 (20200201); C08F
10/00 (20130101); C07D 207/27 (20130101); C08F
220/1808 (20200201); C08F 10/00 (20130101); C08F
4/28 (20130101); C10M 2227/061 (20130101); C10M
2215/26 (20130101); C10M 2217/024 (20130101); C10M
2221/04 (20130101); C10M 2215/04 (20130101); C10M
2223/12 (20130101); C10M 2217/06 (20130101); C10M
2209/084 (20130101); C10M 2217/046 (20130101) |
Current International
Class: |
C07D
207/27 (20060101); C07D 207/00 (20060101); C07D
233/16 (20060101); C07D 265/00 (20060101); C07D
265/32 (20060101); C07D 233/00 (20060101); C08F
10/00 (20060101); C08F 220/00 (20060101); C08F
220/18 (20060101); C07G 069/54 () |
Field of
Search: |
;260/486R,482 |
Other References
riddle, E. H., "Monomeric Acrylic Esters" Reinhold Pub. Corp.,
1954, pp. 92-93. .
Doak, J.A.C.S. 72, 4681 (1950)..
|
Primary Examiner: Killos; Paul J.
Claims
We claim:
1. An oligomer of
a. about 10 to about 90 weight percent of a 1-alkene, or of a
mixture of 1-alkenes, all having 4 to 32 carbon atoms;
b. about 1 to aout 35% of a compound or compounds having the
formula: ##EQU7## wherein X is hydrogen or a methyl group, and R is
a straight or branched chain alkyl group having 8 to 34 carbon
atoms, and;
c. 1 to about 35% of a compound or compounds having the formula:
##EQU8## wherein R.sub.2 is hydrogen or a methyl group, and R.sub.3
is (CH.sub.2 --).sub.n X, wherein n is an integer ranging in value
from 0 to 8, and X is CO.sub.2 R.sub.4 where R.sub.4 is any alkyl
group having 1 to 4 carbon atoms.
2. An oligomer of claim 1 wherein from about 40 to 85 weight
percent is derived from said 1-alkenes.
3. Oligomeric compositions according to claim 1, comprising
oligomers with number-average molecular weight in the range of from
1000 to 4000.
Description
BACKGROUND OF THE INVENTION
The known techniques for preparing 1-alkene containing copolymers
yield products which have a wide molecular weight diversity and an
extreme compositional heterogeneity. While the copolymers formed
may display some beneficial properties, the overall effect of using
a given amount of the polymer will be diminished by that part of
the product having a molecular weight or composition which
possesses detrimental or non-useful qualities. Thus, in order to
produce a polymer in which the good qualities are concentrated so
that less of the polymer need be used to accomplish a desired
effect, it would be desirable to employ a polymerization technique
which would allow for such control of polymer molecular weight and
composition so that most of the polymeric material produced would
have the beneficial qualities sought.
The prior art discloses a series of amide-containing copolymers
which are disclosed as useful as additives to oil, to wit, Bondi
U.S. Pat. No. 2,800,452 (filed July 1954), and Newey U.S. Pat. No.
2,912,416 (also filed July 1954). They do not, however, teach or
suggest the presently disclosed 1-alkenes-alkyl acrylates higher
alkyl acrylate oligomers, which have superior sludge dispersant
properties.
The U.S Pat. No. 2,912,416 recites an amide-containing copolymer
based on components which cannot produce the presently taught
oligomers.
Similarly, the U.S. Pat. No. 2,800,452 does not include the higher
alkyl acrylate components of the type contemplated for use in the
presently taught oligomers; rather, it intended to exclude long
chain esters, which we have discovered contribute significantly to
the here-desired oil-solubility and/or dispersancy of the resulting
oligomer.
Indeed, it can fairly be said that the cited patents actually lead
away from using higher alkyl acrylates, in view of their statements
that such components are undesirably hydrolytically unstable.
THE INVENTION
Accordingly, it is an object of the invention to provide a novel
process for making oligomers.
Another object of the invention is to provide novel oligomers and
oligomeric products comprising these oligomers.
A further object of the invention is to provide novel oligomers
containing 1-alkenes and higher alkyl derivatives of acrylic acids
and having a narrow range of molecular weight and high
compositional homogeneity.
Still another object of the invention is to provide novel additives
for lubricating oils which are useful as low temperature and
ashless sludge dispersants and detergents. These and other objects
will be apparent from the specification and claims.
It has now been found that these and other objects may be
accomplished by oligomers which are produced by an oligomerization
process which comprises the continuous addition of at least one
derivative of an acrylic acid to a mixture of a free radical
initiator and at least one alkene-1 having 4 to 32 carbon atoms or
more, in which the addition is carried out at such a rate that the
substantially instantaneous mole ratio in the reaction mixture of
the derivative to the alkene-1 is maintained relatively constant at
from about 0.01 to about 0.20 during the addition. At a given
reaction temperature and catalyst concentration, the molecular
weight of the oligomer produced will be directly related to the
mole ratio of the acrylic acid derivative(s) to the alkene-1.
Varying this mole ratio between 0.01 and 0.20 will give oligomers
having a degree of polymerization of about 4 to about 35.
When the resulting oligomeric products of the invention are added
to lubricating oils, they show activity as low temperature sludge
dispersants and as detergents. Since oligomers produced by the
process of the invention have relatively uniform molecular weight
and composition, the effect of a given amount of the oligomer as a
sludge dispersant or detergent can be heightened by suitable
control of molecular weight and composition.
One of the advantages of the invention is that the molecular weight
of the oligomer can be controlled, to give a product having a
molecular weight falling within a narrow range, by adjusting the
rate of addition of the acrylic derivative, in order to maintain a
specified mole ratio of arylic derivative to alkene-1 in the
reaction mixture.
In producing the compounds which are useful as additives to
lubricating oils, the oligomers of the invention may be
post-reacted with alcohols, esters, or amines to form new
oligomeric products. Among the post-reactions which are especially
useful are the reaction of an ester of an acrylic acid with an
alcohol to give a new acrylic ester through transesterification or
with an amine to give an acrylic amide through aminolysis, the
reaction of an acrylic acid with an alcohol to give an acrylic
ester, and the reaction of an alkyl nitrile with an ethylenediamine
to give an imidazoline.
Furthermore, a third monomer co-oligomerizable with the acrylic
acid derivative and the alkene-1 may be added prior to the addition
process, either to the acrylic derivative or to the alkene-1, thus
forming a co-oligomer of the acrylic derivative, alkene-1 and said
third monomer. Both of the above variations in the polymerization
process of the invention are useful for introducing valuable
modifications into the oligomers of the invention.
The novel oligomers of the invention are oligomers of:
a. about 10 to 90% by weight of a 1-alkene or a mixture of
1-alkenes;
b. about 1 to 45% by weight of a straight or branched chain alkyl
acrylate or methacrylate in which the alkyl group contains 8 to 34
carbon atoms, and;
c. 1 to about 35% by weight of an acrylic acid, ester or nitrile,
or an amide or an amino derivative of an acrylic acid, or a mixture
of such acids, esters, nitriles, and amido and amino
derivatives.
The first component of the oligomers of the invention is an olefin
of the following Formula I: ##EQU1## wherein R.sub.1 is alkyl, and
R.sub.2 is H or alkyl.
Any polymerizable terminal olefin having 4 to 32 carbon atoms or
more which will oligomerize with one of the acrylic acid
derivatives can be used in the oligomerization process of the
invention. Mixtures of such alkenes can also be used.
Among the purposes of the alkene-1 are the following: to confer a
high degree of oil-solubility upon the oligomer, as well as close
control over the molecular weight. Examples of such oligomerizable
olefins desirable for this purpose include: butene-1, pentene-1,
hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1,
dodecene-1, tridecene-1, tetradecene-1, pentadecene-1,
hexadecene-1, heptadecene-1, octadecene- 1, nonadecene-1,
eicosene-1, tetracosene-1, pentacosene-1, hexacosene-1,
heptacosene-1, nonacosene-1, triacontene-1, hentriacontene-1,
dotriacontene-1, and the like. Also useful are branched-chain
alkenes such as vinylcyclohexane, 3,3-dimethylbutene-1,
3-methylbutene-1, diisobutylene 4-methylpentene-1, and the
like.
Likewise useful in this invention are alkene-1's having 10 to 32
carbon atoms, derived from the polymerization of ethylene,
propylene, or mixtures thereof, which in turn are commercially
provided from hydrocracked stocks.
The second component of the oligomers of the invention is an
acrylic ester of the following formula II: ##EQU2## where X is
hydrogen or methyl, and R is a straight or branched chain alkyl
group having 8 to 34 carbon atoms.
Mixtures of the compounds of formula II can also be used. Examples
of such compounds include: 2-ethylhexyl acrylate, isodecyl
acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate,
tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate,
dodecyl-pentadecyl acrylate, hexadecyl acrylate, heptadecyl
acrylate, octadecyl acrylate, cetylstearyl acrylate, oleyl
acrylate, nonadecyl acrylate, eicosyl acrylate, cetyl-eicosyl
acrylate, stearyl-eicosyl acrylate, docosyl acrylate,
eicosyl-tetratriacontyl acrylate, and the like.
The third component of the oligomers of the invention is a compound
of the following formula III: ##EQU3## wherein R.sub.1 may be H,
CO.sub.2 H or CO.sub.2 R.sub.4 (R.sub.4 is an alkyl group having 1
to 4 carbon atoms);
R.sub.2 is (CH.sub.2) X, wherein n is an integer ranging in value
from 0 to 8, and
R.sub.3 is hydrogen or methyl.
X may be halogen, --CO.sub.2 H, --C .tbd. N, --CO.sub.2 R.sub.5
(R.sub.5 may be any alkyl groups having 1 to 4 carbon atoms or it
may be a polar moiety containing ether or sulfide or sulfinyl or
hydroxyl or amine or amide groups or combinations thereof and the
like, (containing as many as 12 carbon atoms), or ##EQU4## (Y is
one of --NZ'Z", --O(CH.sub.2).sub.n NZ'Z",
.quadbond.O(CH.sub.2).sub.n CONZ'Z", --NHNZ'Z" or
--N.sup.-N.sup.+Z.sub.3 "
wherein
n is a whole positive integer from 1 to 12,
Z' is hydrogen or an alkyl group straight or branched of 1 to 20
carbon atoms,
Z" is hydrogen or an alkyl group of 1 to 20 carbon atoms
Z'" is an alkyl group of 1 to 4 carbon atoms, and
Z' and Z" can be taken together to form an azacycloalkyl ring, an
azacycloalkanone ring, a carbalkoxyazacycloalkanone ring, an
oxaazacycloalkyl ring, an oxaazacycloalkanone ring or a
diazacycloalkanone ring);
X may also be N-pyrrolidinyl and the like;
R.sub.1 and R.sub.2 together may be an anhydride group.
Among the compounds of formula III an acrylic acid, methacrylic
acids or derivatives thereof. Also included are suitably
substituted polymerizable olefins which may be used to introduce
into the oligomer functional groups to be subsequently transformed
into dispersant sites by reaction with amines and polyamines,
esters, alcohols and aminoalcohols; or which may be derivatized
with these compounds.
Examples of such substituted oligomerizable olefins include:
4-chlorobutene-1, 4-pentenonitrile, 4-pentenoic acid, methyl
4-pentenoate, ethyl 4-pentenoate, 5-hexenoic acid, 6-bromohexene-1,
10-undecenoic acid, methyl 10-undecenoate, and ethyl
10-undecenoate, and 4-pentenamides.
Mixtures of the compounds of formula III may also be used. Examples
of such compounds include: acrylic acid, methacrylic acid, methyl
acrylate, methyl methacrylate, methyl chloroacrylate, ethyl
acrylate, propyl acrylate, n-butyl, acrylate, acrylonitrile,
1-(methacryloxyethyl)-2-pyrrolidinone,
1-(methacryloxyethoxyethyl)-2-pyrrolidinone and the like.
Other examples are methylthioalkyl acrylate (alkylene group is
C.sub.1-9), ethylthioalkyl acrylate (alkylene group is C.sub.1-8),
alkylthioethyl acrylate (alkyl group is C.sub.1-8) and
alkylsulfinylalkyl acrylates, in which the alkyl and alkylene
groups together contain no more than ten carbon atoms,
alkylthiopolyethoxyethyl acrylates containing one to four
oxyethylene groups, alkylthiopolypropyloxypropyl acrylates
containing one to three oxypropylene groups,
alkylsulfinyl-polyethoxyethyl acrylates containing one to four
oxyethylene groups, alkylsulfinylpolypropyloxypropyl acrylates
containing one to three oxypropylene groups (in each of the
foregoing, the total number of carbon atoms of R.sub.5 group is no
more than ten), and the like.
Other examples of such derivatives include methacrylamide,
acrylamide, N-methylacrylamide, N-ethylacrylamide,
N-ethylacrylamide, N-butanolacrylamide,
2-(N-morpholino)ethylacrylamide, N,N-dimethylacrylamide,
N,N-diethylacrylamide, N-t-butylacrylamide,
N,N-di-n-butylacrylamide, N-(2-acryloxyethyl)-morpholinone-2-,
N-(2-methacryloxyethyl)-morpholinone-2,
N-(2-methacryloxyethyl)-5-carbo-n-butoxypiperidinone-2,
2-(N,N-dimethylamino)ethyl acrylate, 3-(N,N-dimethylamino)propyl
acrylate, 2-(N-t-butylamino)ethyl acrylate,
2-(N,N-dimethylamino)ethyl methacrylate, and
3-(N,N-dimethylamino)propyl methacrylate.
Two processes can be used in producing the oligomers of the
invention. The first process comprises the continuous addition of
at least one compound of both Formulas I and II, to at least one
compound of Formula III that is already a dispersant monomer.
The addition is carried out at such a rate that the substantially
instantaneous mole ratio in the reaction mixture of compounds of
Formulas II and III to compounds of Formula I is maintained
relatively constant at from about 0.01 to about 0.20 during the
addition. A free radical initiator is mixed with the Formula II
compound, or Formula I compound, or both, prior to the
addition.
In the second process for producing the oligomer of the invention,
an oligomer produced by the continuous addition of at least one
compound of Formulas II and III to at least one compound of Formula
I, by a process similar to that described above, is post-reacted
with an alcohol or an amine. Thus, when an acrylic acid or an
acrylic ester is used as a starting monomer (that is, when R.sub.1
is H and R.sub.2 is --CO.sub.2 H or --CO.sub.2 R.sub.4 in Formula
III,) or when a substituted 1-olefin bearing an acid or ester group
is employed, the acid groups or the ester groups in the oligomer
can be post-reacted with an alcohol or an amine having the formula
HZ'", wherein Z'" is as defined in Formula III, or these groups can
be neutralized or hydrolyzed with a base to form a salt of an
acrylic acid. The relative amounts of the reactants can be chosen
so that any desired percentage of the acid or ester groups can be
converted to the desired derivative.
Among the alcohols and amines which may be post-reacted with the
acid or ester groups in the oligomer are
N-hydroxyethylmorpholinone-2, N-hydroxyethylpyrrolidone,
N,N-dimethylaminoethylamine, 5-aminopentylimidazoline,
diethylenetriamine, aminoethylethylene urea,
2-(2-aminoethyl)-aminoethanol, triethylenetetramine,
tetraethylenepentamine and N,N-dimethylaminopropylamine.
Besides these useful post-reactions we have found the reaction of
multifunctional alcohols and amines with carboxylic acid groups
present in oligomers (to form esters, or amides or amine salts) to
be a most effective way of introducing into the oligomers polar
groups with detergent, dispersant and/or anti-oxidant activity. The
carboxylic acid groups may be provided, for example, by the use of
acrylic acid, 4-pentenoic acid or 10-undecenoic acid as
monomers.
Such alcohols and amines include ethylene glycol, diethylene
glycol, triethylene glycol, glycerol, sorbitol, erythritol,
trimethylene glycol, pentaerythritol, C.sub.4-12 -alkyl glucosides,
alkylthioalkanols and alkylsulfinylalkanols, where the alkyl and
alkylene groups have one to twelve carbons, 2,2'-thiodiethanol,
2,2'-sulfinyldiethanol, diethanolamine, triethanolamine,
N-methyldiethanolamine, diglycolamine, N-methylformamide,
glucosylamine, N-(.beta.-hydroxyethyl)-morpholine,
N-(.beta.-hydroxyethyl)-morpholinone,
2-(2-aminoethylamino)-ethanol, N-(2-hydroxyethyl)-piperazine,
1-(.beta.-hydroxyethyl)-2-pyrrolidinone,
1-(hydroxyethoxyethyl)-2-pyrrolidinone,
N,N-dimethylaminopropylamine, N-(2-aminoethyl)-ethyleneurea,
N-(2-aminoethyl)-piperazine, calcium N-methyl-taurate,
ethylenediamine, diethylenetriamine, triethylene-tetramine,
tetraethylenepentamine and pentaethylenehexamine.
Also, oligomeric carboxylic acids or their methyl or ethyl esters,
having been post-reacted with diethylene triamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, etc., may be further reacted with one to
five equivalents of methyl or ethyl formate, methyl or ethyl
acetate, ethylene oxide or propylene oxide, phosphorus
pentasulfide, carbon disulfide, acrylo-or acetonitrile giving
corresponding formamides, acetamides, hydroxyethyl or
hydroxypropyl, thiophosphoramide, thiocarbamate, 2-cyanoethyl or
imidazoline derivatives.
Any suitable catalyst may be used in the production of the
copolymers of the invention. Among the preferred catalysts are
peroxide catalysts, such as, for example, benzoyl peroxide, lauroyl
peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide,
2,2-bis-(tertiary butylperoxy)-butane, di-(tertiary butyl)peroxide,
tertiary butyl perpelargonate, tertiary-butyl perbenzoate, hydrogen
peroxide, and percarbonates, peracetic acid, and the like. The
amount of catalyst which is added will vary, depending on the
monomers employed as starting materials, reaction temperature,
degree of polymerization desired, etc., but generally the catalyst
will be present at about 0.01 to 10% by weight of the material
being polymerized, and preferably will be present at about 0.1 to
1.0 percent by weight.
The temperature at which the oligomerization reaction is run can
also be varied over a broad range, and any temperature which will
not impair the oligomerization can be selected. A preferred
reaction temperature range is from about 100.degree.C. to
200.degree.C. While the choice of catalyst and reaction temperature
may be used to exert some control over the molecular weight of the
oligomers produced according to the invention, the major factor
which determines the copolymer molecular weight is the mole ratio
of the acrylic acid derivative to the alkene-1, as described
above.
In a preferred embodiment of the invention, the alkene-1 mixture
and the acrylic acid derivatives will contain an alkyl chain of
sufficient average length to impart oil-solubility to the oligomer.
Among the monomers which are particularly useful in making
oil-soluble oligomer are those having alkyl chains averaging 8
atoms or more, such as tetradecene-1, n-dodecyl acrylate, and the
like.
When the oligomeric products of the invention are added to
lubricating oils, they show activity as low temperature sludge
dispersants and as detergents. Since oligomers produced by the
process of the invention have relatively uniform molecular weight
and composition, the effect of a given amount of the polymer as a
sludge dispersant or detergent can be heightened by suitable
control of molecular weight and composition.
One of the advantages of the invention is that the molecular weight
of the oligomer can be controlled, to give a product having a
molecular weight falling within a narrow range of distribution, by
adjusting the rate of addition of the acrylic derivative in order
to maintain a specified mole ratio of acrylic derivative to
alkene-1 in the reaction mixture.
The following working examples illustrate syntheses within the
teaching of the present invention which may be employed in
formulating the compositions of the invention but are not
considered limiting the invention described heretofore.
EXAMPLE I
Preparation of Oligomer:HD/DPA/AA/58.3/21.1/20.6
Into a 12-liter, 3-necked, round-bottom flask fitted with a
motor-driven C-stirrer, thermometer, reflux condenser and a 1000-ml
graduated dropping addition funnel is added 6207 g. (27.66 moles)
of 1-hexadecene (HD) from Gulf Oil Corp. The alkene is heated with
stirring in a nitrogen atmosphere to 132.degree. and 7.30 g.
(0.0319 mole) of 85% t-butyl perbenzoate in xylene is added
rapidly. A total of 497.7 g. (2.28 moles) of dodecyl-pentadecyl
acrylate (DPA), 694.0 g. (9.63 moles) of acrylic acid (AA), and
4.44 g. (0.0194 mole) of 85% t-butyl perbenzoate is blended and
charged to the dropping addition funnel; and addition of
acrylate/acrylic acid is carried out at a constant rate for 6.38
hours. The pot temperature is maintained at 132.degree.-135.degree.
with moderate stirring for 16 hours. The temperature is then raised
to 192.degree., and unreacted monomers are distilled under
gradually reduced pressure to 1 mm Hg. After 45 minutes at
192.degree./1 mm Hg the residue is cooled to 130.degree. and
weighed. After a sample had been removed for analysis, the
remaining oligomer was diluted to a 52.0% solution with 100 neutral
oil in order to confer acceptable fluidity upon the product.
In a typical preparation, the amount of oligomer produced was
3001.5 g. (a 40.0% yield); it was found to have the composition
HD/DPA/AA//58.3/21.1/20.6 and a number-average molecular weight of
3200 .+-. 10.
EXAMPLE IIA
Preparation of the Oligomer:TD/DPA/AA//49.7/27.8/22.5
A 12-liter, 3-necked, round-bottom flask is charged with 5265 g.
(26.8 moles) of commercial tetradecene (92-93% 1-tetradecene) and
is then fitted with a motor-driven Trubore C-stirrer, a candlestick
adapter holding a thermometer and a 1-liter graduated dropping
addition funnel, and a reflux condenser. The alkene is heated with
stirring in an atmosphere of nitrogen to 132.degree.C. A total of
6.20 g. of t-butyl perbenzoate is added directly and five minutes
later the continuous addition of a solution of 1310 g. (5.00 moles)
of dodecyl-pentadecyl acrylate, 1035 g. (14.36 moles) of acrylic
acid and 8.28 g. of t-butyl perbenzoate is begun via the dropping
addition funnel. With the reaction temperature maintained at
132.degree.-133.degree., the addition of acrylate solution is
completed in 4.75 hours; the product mixture is held at 132.degree.
(with stirring) for 16 hours. The temperature is then raised to
192.degree. and unreacted monomers are distilled under gradually
reduced pressure to 1 mm Hg pressure. After 45 minutes at
192.degree./1 mm Hg, the residue is cooled to 135.degree. and
weighed. After a sample of oligomer has been removed for analysis,
the remainder is diluted to 55% with 100 neutral oil to give a
product with acceptable fluidity at room temperature.
In a typical preparation, the weight of oligomer produced was 4458
g. (a 58.6% yield); it was found to have the composition
TD/DPA/AA//49.7/27.8/22.5 and a number-average molecular weight of
4240 .+-. 10, and diluted to a 52.0% solution with 100 neutral
oil.
EXAMPLE IIB
The Esterification of TD/DPA/AA//49.7/27.8/22.5; (M.sub.n = 4240
.+-. 10) with 2,2'-Sulfinyldiethanol
To a 2-liter, 3-necked round-bottom flask fitted with a
motor-driven C-stirrer, thermometer and a Dean-Stark trap connected
to an Allihn condenser, are added 477.3 g. (0.8207 equiv., based on
AA) of a 52.0% solution of the TD/DPA/AA oligomer of Ex. IIA in 100
neutral oil, 138.2 g. (1.000 mole) of 2,2'-sulfinyldiethanol and
400 ml of xylene. The mixture is heated under gentle reflux
(152.degree.-153.degree.) with moderate stirring for 6 hours, with
water removed as it formed.
The product mixture is cooled to 105.degree. and diluted with 272.2
g. of 100 neutral oil. Xylene is removed by strip-distillation to
150.degree./2 mm Hg. The product and unreacted
2,2'-sulfinyldiethanol are partitioned between hexane and 16%
aqueous magnesium sulfate solution. Water is removed from the
solution of product by azeotropic distillation and hexane is
removed by strip-distillation to 135.degree./2 mm Hg. Analysis of a
typical product indicated that the extent of esterification was
37%.
A reaction product of the above ester and 2,2'-sulfinyldiethanol,
in which 43% esterification was achieved, attained a sludge rating
of 37.2 (50.0 = clean), and a varnish rating of 33.6 (50.0 = clean)
in the MS Sequence V-B test after 192 hours.
EXAMPLE III
The Preparation of HD/DPA/AA//59.8/24.0/16.2
To a 12-liter, 3-necked, round-bottom flask fitted with a
motor-driven C-stirrer, thermometer, reflux condenser and two
graduated dropping addition funnels is added 3250.0 g. (14.48
moles) of 1-hexadecene. The alkene is heated with stirring in a
nitrogen atmosphere to 164.degree. and a mixture of 14.9 g. (0.057
mole) of dodecyl-pentadecyl acrylate, 9.1 g. (0.13 mole) of acrylic
acid and 4.5 g. (0.022 mole) of dodecyl mercaptan is added rapidly.
To one addition funnel is charged a mixture of 445.0 g. (1.70
moles) of dodecylpentadecyl acrylate and 286.0 g. (3.97 moles) of
acrylic acid, and to the other addition funnel is added a 400.0 g.
(1.78 moles) of 1-hexadecene and 7.6 g. (0.033 mole) of 85% t-butyl
perbenzoate in xylene. The contents of each addition funnel are
added simultaneously at a constant rate over 7.54 hours with the
pot temperature maintained at 160.degree.-164.degree. .
Upon completion of addition of acrylate/acrylic acid and solution
of initiator the reaction mixture is allowed to cool with stirring
to 132.degree. overnight (16 hours.) The temperature is then raised
to 192.degree. and unreacted monomers are distilled under gradually
reduced pressure to 1 mm Hg. After 45 minutes at 192.degree./1 mm
Hg the residue is cooled to 135.degree. and diluted to a 54.9%
solution with 100 neutral oil.
In a typical preparation, the weight of oligomer produced was
1728.3 g. (a 39.2% yield). It was found to have the composition
HD/DPA/AA//59.8/24.0/16.2 and a number-average molecular weight of
2030 .+-. 20.
EXAMPLE IV
Synthesis of the Oligomer:HD/DPA/MU//22.5/58.2/19.3
Into a 12-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser and
1-liter graduated dropping addition funnel are charged 2074.2 g.
(9.242 moles) of 1-hexadecene and 1319.9 g. (6.656 moles) of methyl
10-undecenoate (MU). The alkene mixture is heated with stirring to
132.degree. in a nitrogen atmosphere and 5.0 g. (0.022 mole) of 85%
t-butyl perbenzoate in xylene is added. A total of 1972.0 g. (7.527
moles) of dodecyl-pentadecyl acrylate and 7.0 g. (0.031 mole) of
85% t-butyl perbenzoate are charged to the dropping addition
funnel; and addition of acrylate is carried out at a constant rate
over 6.13 hours with the pot temperature maintained at
132.degree.-135.degree. .
Upon completion of addition of acrylate, heating is continued at
132.degree.-134.degree. with moderate stirring for 16 hours. The
pot temperature is then raised to 193.degree. and unreacted
monomers are distilled under gradually reduced pressure to 2 mm Hg.
After 45 minutes at 193.degree./2 mm Hg the residue is cooled to
room temperature in a nitrogen atmosphere.
In a typical preparation, the weight of product was 3121.9 g. (a
58.2% yield.) The oligomer was found to have the composition
HD/DPA/MU//22.5/58.2/19.3 with a number-average molecular weight of
3020 .+-. 15.
EXAMPLE V
Synthesis of the Oligomer: HD/DPA/MP//27.9/62.0/10.1
Into a 12-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser and
1-liter graduated dropping addition funnel are charged 2468.8 g.
(11.00 moles) of 1-hexadecene and 1009.3 g. (8.842 moles) of methyl
4-pentenoate (MP). The alkene mixture is heated with stirring to
132.degree., in a nitrogen atmosphere, and 5.11 g. (0.0224 mole) of
85% t-butyl perbenzoate in xylene is added. A total of 2206.0 g.
(8.420 moles) of dodecyl-pentadecyl acrylate and 7.79 g. (0.0341
mole) of 85% t-butyl perbenzoate are charged to the dropping
addition funnel; and addition of acrylate is carried out at a
constant rate over 8.25 hours with the pot temperature maintained
at 132.degree.-134.degree.. Upon completion of addition of
acrylate, heating is continued at 132.degree.-134.degree. with
moderate stirring for 15 hours. The pot temperature is then raised
to 192.degree. and unreacted monomers are distilled under gradually
reduced pressure to 1 mm Hg. After 45 minutes at 192.degree./1 mm
Hg the residue is cooled to room temperature in a nitrogen
atmosphere.
In a typical preparation, the weight of product was 3556.7 g. (a
62.6% yield). The oligomer was found to have the composition
HD/PPA/MP//27.9/62.0/10.1 with a number-average molecular weight of
2875 .+-. 75.
EXAMPLE VI
The Reaction of the Oligomer of Example V with
Diethylenetriamine
To a 2-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer and reflux-distillation
head are added 400.0 g. (0.347 equiv., based on MP) of the oligomer
of Ex. V and 62.0 g. (0.601 mole) of technical-grade
diethylenetriamine. The reaction mixture is heated with moderate
stirring at 150.degree.-155.degree. for 6 hours in a nitrogen
atmosphere and methanol is removed as formed. The product mixture
is diluted with 400.0 g. of 100 neutral oil and unreacted amine is
strip-distilled at 155.degree. with the pressure gradually reduced
to 3 mm Hg.
The product is cooled to room temperature in an atmosphere of
nitrogen. In a typical preparation, a total of 802 g. of product,
containing 1.52% nitrogen, was recovered. Analytical data indicated
that 73.9% of the carbomethoxy groups from MP had been
amidated.
This material attained a sludge rating of 35.0 (50.0 = clean) and a
varnish rating of 37.8 (50.0 = clean) in the MS Sequence V-B test
(see ASTM Special Technical Publication No. 315-D) test after 192
hours. Under similar test conditions OLOA 1200 (a polybutane-based
succinimide) a commercial product marketed by Socal, Oronite
Division, achieved a sludge rating of 35.1 and a varnish rating of
31.2.
EXAMPLE VII
The Synthesis of the Oligomer: HD/DPA/MA//52.1/39.7/8.2
To a 2-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser,
125-ml graduated dropping addition funnel and a 250-ml graduated
dropping addition funnel is added 589.6 g. (2.627 moles) of
1-hexadecene. The alkene is heated in a nitrogen atmosphere at
185.degree. with moderate stirring. A total of 1.615 g. (0.0106
mole) of cumene hydroperoxide in 6.01 g. (0.022 mole) of
1-hexadecene is added rapidly. Seventeen minutes later the
simultaneous but separate additions of a solution of 245.0 g.
(0.935 mole) of dodecylpentadecyl acrylate and 65.3 g. (0.763 mole)
of methyl acrylate (MA) and a solution of 1.256 g. (0.00825 mole)
of cumene hydroperoxide in 25.0 g. (0.111 mole) of 1-hexadecene are
begun.
The continuous additions of monomers and initiator are carried out
at a constant rate, so that after 7.06 hours the addition of
acrylate monomers is complete, while that of initiator is 97%
complete. The remaining initiator is added rapidly and the reaction
mixture is allowed to cool to 132.degree. over the space of 16
hours with moderate stirring. The product mixture is heated at
190.degree. for 1.5 hours with moderate stirring in a nitrogen
atmosphere and then unreacted monomers are removed by
strip-distillation at 190.degree. with the pressure gradually
reduced to 3.5 mm Hg. The residue is then cooled to 60.degree. in a
nitrogen atmosphere and clarified by filtration.
In a typical preparation, the weight of product was 608.8 g. (a
65.4% yield); the oligomer was found to have the composition
HD/DPA/MA//52.1/39.7/8.2 with a number-average molecular weight of
1625 .+-. 10.
EXAMPLE VIII
The Reaction of the Oligomer: HD/DPA/MA//51.8/38.1/10.1 with
Triethylenetetramine
To a 3-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer and reflux-distillation
head are added 350.0 g. (0.4102 equiv., based on MA) of the
oligomer and 73.2 g. (0.501 mole) of triethylenetetramine. The
mixture is heated at 140.degree. with moderate stirring in a
nitrogen atmosphere for 8 hours. It is then cooled to 120.degree.
and diluted with 350.0 g. of 100 neutral oil, 300 ml. of toluene
and 300 ml. of isobutyl alcohol. A total of 100.0 g. (0.350 equiv.
H.sup.+) of Amberlyst 15 resin beads is added and the mixture is
stirred slowly overnight at ambient temperature. The mixture is
then stirred in a nitrogen atmosphere at 85.degree. for one hour
and is cooled and filtered. Solvents and traces of unsequestered
triethylenetetramine are removed by strip-distillation to
125.degree. with the pressure gradually reduced to 1.5 mm Hg. The
product is cooled in an atmosphere of nitrogen.
In a typical preparation the product, which had a base number of
47.4 and contained 1.68% nitrogen, was amidated at 48.7% of the
carbomethoxy groups from MA and 3.6% of the carboalkoxy groups from
DPA. This material attained a sludge rating of 36.2 (50.0 = clean)
and a varnish rating of 32.1 (50.0 = clean) in the MS Sequence V-B
test after 192 hours. Under similar test conditions, OLOA-1200 a
commercial product (a polybutene-based succinimide) marketed by
Socal, Oronite Division, achieved a sludge rating of 35.1 and a
varnish rating of 31.2
EXAMPLE IX
The Reaction of Ethyl Formate with the Oligomer HD/DPA/MA//
50.3/39.8/9.9 Previously Condensed with Triethylenetetramine
To a 2-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux-distillation
head and 125 ml. dropping addition funnel is added 771.7 g. (0.486
equiv. of primary amine) of the amidated oligomer. This material is
the condensation product of the oligomer (HD/DPA/MA//50.3/39.8/9.9;
M.sub.n = 1745 .+-. 15) and triethylenetetramine, in which 45.4% of
the carbomethoxy groups from MA and 19.6% of the carboalkoxy groups
from DPA had been amidated. The oligomer is heated with moderate
stirring to 88.degree. in an atmosphere of nitrogen, and 42.4 g.
(0.572 mole) of ethyl formate is added dropwise over the space of
10 minutes. Heating is continued at 88.degree. for 2 hours.
Volatile material is stripped at 90.degree. with the pressure
gradually reduced to 1 mm Hg. The product is then cooled in an
atmosphere of nitrogen. In a typical preparation, a total of 0.432
equiv. of amine are formylated.
A formulated oil containing 1.20% of this product as the sludge
dispersant showed 11% top-groove fill after 240 hours in the
Caterpillar 1-H test. The same oil lacking a dispersant showed 36%
top-groove fill after 240 hours.
EXAMPLE X
The Synthesis of the Oligomer: HD/CEA/MA//48.7/41.7/9.6
To a 3-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser,
125-ml. graduated dropping addition funnel and a 1-liter graduated
dropping addition funnel are added 901.3 g. (4.016 moles) of
1-hexadecene. The alkene is heated in a nitrogen atmosphere at
185.degree. with moderate stirring. A total of 0.90 g. (0.0059
mole) of cumene hydroperoxide in 10.0 g. of tridecane is added
rapidly. Ten minutes later the simultaneous but separate additions
of a solution of 280.0 g. (0.8578 mole) of cetyl-eicosyl acrylate
(CEA) and 77.4 g. (0.899 mole) of cumene hydroperoxide in 50.0 g.
of tridecane are begun. The continuous additions of monomers and
initiator proceeds at a constant rate and is completed after 6.93
hours.
The reaction mixture is allowed to cool to 132.degree. over the
space of 17 hours with moderate stirring. The product mixture is
then heated to 192.degree. and unreacted monomers are removed by
strip-distillation at 193.degree. with the pressure gradually
reduced to 3 mm Hg. The residue is cooled to room temperature in an
atmosphere of nitrogen and is clarified by filtration.
In a typical preparation, the weight of product was 662.9 g. (a
52.7% yield); the oligomer was found to have the composition
HD/CEA/MA//48.7/41.7/9.6 with a number-average molecular weight of
1425 .+-. 25.
EXAMPLE XI
The synthesis of the Oligomer: OD/DPA/MA//65.0/14.3/20.7
To a 5-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser, 125
ml. graduated dropping addition funnel and a 1-liter graduated
dropping addition funnel is added 2424.9 g. (9.604 moles) of
1-octadecene. The alkene is heated at 185.degree. with moderate
stirring in a nitrogen atmosphere. A total of 0.8169 g. (0.00537
mole) of cumene hydroperoxide in 25.0 g. (0.099 mole) of
1-octadecene is added rapidly. Seventeen minutes later the
simultaneous but separate additions of a solution of 262.0 g. (1.00
mole) of dodecylpentadecyl acrylate, and 416.6 g. (4.737 moles) of
methyl acrylate, and a solution of 4.5322 g. (0.02978 mole) of
cumene hydroperoxide in 75.0 g. (0.297 mole) of 1-octadecene are
begun.
The continuous addition of monomers and initiator proceeds at a
constant rate and after 7 hours the addition of acrylate monomers
is complete, while that of initiator is 93.3% complete. The
remaining initiator is added rapidly and heating at 185.degree. is
continued for 1 hour. The reaction mixture is allowed to cool
overnight (16 hours) to 130.degree. with moderate stirring.
Unreacted monomers are removed by strip-distillation at 210.degree.
with the pressure gradually reduced to 1 mm Hg. The residue is
cooled to room temperature in an atmosphere of nitrogen and is
clarified by filtration.
In a typical preparation, the weight of product was 1835.6 g. (a
57.3% yield); the oligomer was found to have the composition
OD/DPA/MA//65.0/14.3/20.7 with a number average molecular weight of
1660 .+-. 40.
EXAMPLE XII
The Reaction of the Oligomer of Example XI with
Triethylenetetramine
To a 3-liter, 4-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer and reflux-distillation
head is added 1660 g. (3.99 equiv., based on MA) of oligomer and
153.5 g. (1.05 mole) of triethylenetetramine. The mixture is heated
at 130.degree. with moderate stirring in an atmosphere of nitrogen
for 8 hours, with methanol distilled upon its formation. Unreacted
amine and other volatile materials are removed by vacuum
strip-distillation to 155.degree./1 mm Hg with intermittent
sparging with nitrogen. The product is cooled in an atmosphere of
nitrogen. In a typical preparation, a total of 1738 g. of product,
with a base number of 67.8 and a nitrogen content of 2.86% was
recovered. Analytical data indicated that 20.7% of the carbomethoxy
groups from MA and 7.7% of the carboalkoxy groups from DPA were
amidated.
A formulated oil containing 1.20% of the product as the sludge
dispersant showed 3% top-groove fill after 409 hours in the
Caterpillar 1-H test. The same oil lacking a dispersant showed 36%
top-groove fill after only 240 hours.
EXAMPLE XIII
The Reaction of Ethylene Oxide with the Oligomer
OD/DPA/MA//65.1/13.9/21.0 Previously Condensed with
Triethylenetetramine
To a 2-liter, 4-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, gas inlet and reflux
condenser (Dewar-type) cooled with acetone-Dry Ice are added 787.6
g. (0.365 equiv. of primary amine) of the title amidated oligomer,
200 ml. of isobutyl alcohol, 100 ml. of isopropyl alcohol and 5.0
ml. of water. This oligomer is the condensation product of the
oligomer OD/DPA/MA//65.1/13.9/21.0 (M.sub.n = 1610 .+-. 15) and
triethylenetetramine, in which 21% of both the carbomethoxy groups
from MA and carbalkoxy groups from DPA have been amidated. The
mixture is heated with vigorous stirring at 70.degree. while 18.0
g. (0.406) moles of ethylene oxide is distilled into the flask over
a 45-minute period.
After holding the product mixture at 70.degree. for 15 minutes,
solvents are distilled at 100.degree. with the pressure gradually
reduced to 1 mm Hg. Quantitative reaction of ethylene oxide is
observed.
A formulated oil containing 1.20% of the product as the sludge
dispersant showed 6% top-groove fill after 240 hours in the
Caterpillar 1-H test. The same oil lacking a dispersant showed 36%
top-groove fill after 240 hours.
EXAMPLE XIV
Reaction of the Oligomer OD/DPA/MA//64.9/14.1/21.0 with
Diethylenetriamine
To a 2-liter, 4-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, stopper and
reflux-distillation head are charged 875.0 g. (2.13 equiv., based
on MA) of the title oligomer and 71.4 g. (0.691 mole) of
diethylenetriamine. The components are heated with moderate
stirring for 8 hours at 140- 142.degree. in an atmosphere of
nitrogen, with methanol distilled upon its formation. Upon
expiration of the reaction time, unreacted amine and other volatile
materials are removed by vacuum strip-distillation to
140.degree.C./1.5 mm Hg pressure with intermittent sparging with
nitrogen. The product is cooled in an atmosphere of nitrogen. A
total of 898.7 g. of product, with a base number of 53.3 and a
nitrogen content of 2.51%, are recovered.
In a typical preparation analytical data indicated that 23.9% of
the carbomethoxy groups from MA and 6.6% of the carboalkoxy groups
from DPA had been amidated.
A formulated oil containing 1.20% of the product as the sludge
dispersant showed 20% top-groove fill after 480 hours in the
Caterpillar 1-H test. The same oil lacking a dispersant showed 36%
top-groove fill after only 240 hours.
EXAMPLE XV
The Synthesis of the Oligomer: HD/DPA/MEOP//36.1/33.6/30.3
To a 2-liter, 3-necked, round-bottom flask fitted with a
motor-driven Trubore C-stirrer, thermometer, reflux condenser, 125
ml. graduated dropping addition funnel and a 1-liter graduated
dropping addition funnel are added 584.5 g. (2.604 moles) of
1-hexadecene. The alkene is heated at 185.degree. with moderate
stirring in a nitrogen atmosphere. A total of 1.615 g. (0.0106
mole) of cumene hydroperoxide in 15.6 g. (0.0696 mole) of
1-hexadecene is added rapidly. Fifteen minutes later the
simutaneous but separate additions of a solution of 245.0 g. (0.935
mole) of dodecyl-pentadecyl acrylate and 188.4 g. (0.758 mole) of
1-(methacryloxyethoxyethyl)-2-pyrrolidinone and a solution of
2.1164 g. (0.0139 mole) of cumene hydroperoxide in 20.5 g. (0.0917
mole) of 1-hexadecene are begun. The continuous addition of
monomers and initiator proceeds at a constant rate. After 7.50
hours, the addition of acrylate monomers is complete, while that of
initiator is 94% complete. The remaining initiator solution is
added rapidly and the reaction mixture is allowed to cool to
130.degree.-132.degree. over the space of 16 hours with moderate
stirring. The product mixture is heated at 190.degree. for 1 hour
in a nitrogen atmosphere with moderate stirring and unreacted
monomers are removed by strip-distillation at 190.degree. with the
pressure gradually reduced to 3 mm Hg. The residue is cooled to
ambient temperature in a nitrogen atmosphere and clarified by
filtration.
In a typical preparation, the weight of product was 556.9 g. (a
52.8% yield). The oligomer, a cherry-red liquid, was found to have
the composition HD/DPA/MEOP// 36.1/33.6/30.3 with a number-average
molecular weight of 1425 .+-. 25.
EXAMPLE XVI
Cooligomerization of Tetradecene-1, Lauryl Acrylate and
N-(B-Acryloxy-ethyl)-Morpholinone-2 (BAEM)
Into a tared 500 ml., three-neck, round bottom flask, equipped with
an air motor-driven stirrer, thermometer, nitrogen inlet tube,
reflux condenser and a 125 ml. pressure equalized graduated
addition funnel were weighed 110 g. of tetradecene-1 and 0.2 g. of
dicumyl peroxide. After an initial deaeration period of
approximately 20 minutes with nitrogen at room temperature, the
variable transformer controlling a heating mantle is turned on
high, and the temperature of the contents of the flask raised to
150.degree.C. A dropwise addition of the contents of the addition
funnel consisting of a homogeneous solution of 84 g. of lauryl
acrylate, 6 g. of BAEM above and 0.8 g. of dicumyl peroxide is then
begun at such a rate that the total addition time is approximately
three hours. The reaction mixture is kept at 150.degree.C. with
stirring and under a nitrogen blanket overnight (fifteen
hours).
After the flask is weight (total weight yield): 201 g.), 183.6 g.
of the reaction mixture are stripped under reduced pressure (up to
about 150.degree.C. at 0.5-1mm. Hg) to give 96.2 g. of oligomer
which corresponds to a weight yield of 52.4%. Analysis of the
unstripped reaction mix by vapor phase chromatography and titration
of the stripped oligomer using a standard perchloric acid solution
in acetic acid gives the following final composition: lauryl
acrylate: tetradecene-1: BAEM 70.3:25.2:4.5 by weight. Kjeldahl
nitrogen analysis gives a value of 0.39% N corresponding to 5.5% by
weight of BAEM in the oligomer. Elemental analysis: ##EQU5##
EXAMPLE XVII
Cooligomerization of Tetradecene-1, 2-Ethyl-hexyl Acrylate and
N-Methacryloxyethyl-N-Methylformamide (MAMF)
Into a tared 500 ml., three-neck, round bottom flask, equipped with
an air motor-driven stirrer, thermometer, nitrogen inlet tube,
reflux condenser and a 125 ml. pressure equalized graduated
addition funnel are weighed 110 g. of tetradecene-1 (Gulf). After
deaerating with nitrogen for about 20 minutes, the tetradecene is
heated to 140 .+-. 5.degree.C. using a heating mantle connected to
a variable transformer. Using a graduated one milliliter pipette,
0.33 ml. of a 70% solution of tertiary butyl hydroperoxide (TBHP)
are added and a dropwise addition of a solution of 74 g. of
2-ethyl-hexyl acrylate, 16 g. of MAMF and 0.66 ml. of 70% TBHP is
begun at such a rate that the addition is finished after about two
hours. About 0.3 ml. of 70% cumene hydroperoxide (=0.1% by weight)
are added and the stirring continued at 135.degree.-140.degree.C.
overnight under nitrogen.
Total weight recovered was 199.6 g. Analysis of the unstripped
reaction mix by vapor phase chromatography showed no residual
2-ethylhexyl acrylate, and oligomer yield of 62.3% and together
with a Kjeldahl nitrogen (0.97%) determination on a stripped sample
indicates an oligomer composition of 2-ethylhexyl
acrylate:tetradecene-1:MAMF = 60.7:28.3:11.8 by weight. A number
average molecular weight determination by thermal tensimetry gave
an average value of 2082. Elemental analysis: ##EQU6##
EXAMPLE XVIII
Cooligomerization of Tetradecene-1, Lauryl Acrylate and 4-Pentenoic
Acid
Into a tared 3000 ml., three-neck, round bottom flask, equipped
with an air motor-driven stirrer, thermometer, nitrogen inlet tube,
reflux condenser and a 500 ml. pressure equalized graduated
addition funnel are weighed 520 g. of tetradecene-1 and 80 g. of
4-pentenoic acid.
Heating and sparging of the flask with nitrogen are started
simultaneously, after 10 minutes, when a temperature of
100.degree.C. is reached, 1.0 ml. of tertiary butyl perbenzoate
(TBPB) is added to the flask. When after an additional 10 minutes a
temperature of 130.degree.C. is reached, a slow addition of a
solution of 2.0 ml. of TBPB in 400 g. of lauryl acrylate is started
at such a rate that the addition is finished in 3 hours. The
reaction mixture is stirred at 130.degree.C. under nitrogen for an
additional 20 hours. The total weight obtained is 1000.5 g., of
which 952.5 g. are stripped under reduced pressure to give 360.0 g.
of distillate and 592.5 g. of oliogmer which corresponds to a yield
of 62.2% by weight. Analysis of an unstripped sample of vapor phase
chromatography (VPC) indicates the following composition for the
oligomer: lauryl acrylate: tetradecene-1:pentenoic acid =
64.2:30.2:5.6 by weight; titration of acidity by standard KOH
solution in isopropanol gave a level of 4.8% pentenoic acid in the
stripped sample. Since this number is not based on differences
between starting and residual concentrations as is the VPC results,
it can be assumed to be more accurate. The oligomer composition is
therefore; lauryl acrylate: tetradecene-1:pentenoic acid =
64.7:30.5:4.8 by weight.
EXAMPLE XIX
Cooligomerization of Tetradecene-1, 2-Ethylhexyl Acrylate and
N-Vinylpyrrolidone (NVP)
Into a tared 500 ml., three-neck, round bottom flask, equipped with
an air motor-driven stirrer, thermometer, nitrogen inlet tube,
reflux condenser and a 125 ml. pressure equalized graduated
addition funnel were weighed 110 g. of tetradecene-1. The flask is
sparged with nitrogen at room temperature for about 40 minutes,
then heated to 110.degree.C. using a heating mantle controlled by a
variable transformer. A solution of 0.1 g. of benzoyl peroxide
dissolved in the minimum amount of ethyl acetate is added and a
dropwise addition of a solution consisting of 76 g. of 2-ethylhexyl
acrylate, 14 g. of N-vinylpyrrolidone is begun. The reaction
temperature is kept between 110.degree.C. and 115.degree.C. and the
addition finished after 3.5 hours. After the addition of 0.33 ml.
of 70% tertiary butyl hydroperoxide, the reaction mixture is kept
at 110.degree.C. under nitrogen and with agitation for 15
additional hours. A total of 206 g. of material is obtained
(including some ethyl acetate). Vapor phase chromatography
indicates a weight yield of approximately 62.5% Kjeldahl nitrogen
on a stripped sample is 1.23% by weight -- this together with the
VPC analysis of the residual monomers gives as a final oligomer
composition: ethylhexyl acrylate: tetradecene:NVP = 61.9:28.4:9.7
by weight. The elemental analysis gave the following results:
C H O N(Kj) 75.22 11.60 12.55 1.23
If the composition is calculated from the elemental analysis, the
ethylhexyl acrylate and tetradecene percentages change to 63.9% and
26.4% respectively. A determination of the number average molecular
weight by thermal tensimetry gave 4291 as the average of three
measurements.
EXAMPLE XX
Reaction of 2-(5-Aminopentyl)Imidazoline with a Cooligomer of
Tetradecene-1, Lauryl Acrylate and Methyl-4-Pentenoate
Into a tared 500 ml., three-neck, round bottom flask, equipped with
an air motor-driven stirrer, thermometer, nitrogen inlet tube and a
Barrett type moisture test receiver fitted with a reflux consenser,
are placed 250 g. of an oligomer of the composition lauryl
acrylate:tetradecene:methyl pentenoate = 66.9:17.4:15.7 by weight
which had been prepared by the same technique as described under
Ex. XVIII and stripped under reduced pressure to remove unreacted
monomer. Enough 2-(5-aminopentyl)imidazoline to equal one-half the
moles concentration of the methyl pentenoate present is added to
the flask (26.8 g.). The contents of the flask are heated to
120.degree.-125.degree.C. and kept at this temperature under
nitrogen with stirring for about 20 hours. After the reaction mix
had cooled slightly, it was poured into a 4-8 fold excess of cold,
reagent grade methanol under through agitation. After a few
minutes, the stirring is stopped and after phase separation the
methanol layer is removed, using a thin glass tube attached to a
suction flask which in turn is connected to a water-operated
aspirator pump. To the methanol-swollen oligomeric material is
added an excess of reagent grade, cold methanol and the same wash
cycle repeated. After a total of 4-methanol wash cycles, the
oligomeric material is transferred to a rotating high vacuum type
evaporator and stripped under reduced pressure to remove all traces
of methanol. A Kjeldahl nitrogen determination gave 1.72% of
nitrogen for the final product which is equal to 6.35% by weight of
the imidazoline and therefore indicates that the reaction yield was
about 66%. The C=O stretching bands appearing in the infrared scan
of the final product taken as a film on a sodium chloride plate are
consistent with amide-formation.
EXAMPLE XXI
Esterification of an Oligomer of Tetradecene-1, Lauryl Acrylate and
4-Pentenoic Acid with N-(.beta.-Hydroxyethyl)-Morpholinone-2
Into a tared 500 ml., three-neck, round bottom flask, equipped with
an air motor-driven stirrer, thermometer and a Barrett type
moisture test receiver fitted with a reflux condenser, are placed
250 g. of the oligomer prepared in Ex. XVIII which had been
stripped and the composition of which is: lauryl
acrylate:tetradecene-1:pentenoic acid = 64.7:30.5:4.8 by weight.
Also added to the flask are 1.2 times the molar equivalent of
pentenoic acid present of
N-(.beta.-hydroxy-ethyl)-morpholinone-2(20.9 g.), and 54 g. of
xylene in order to facilitate the removal of the water produced.
Using a heating mantle controlled by a variable transformer, the
contents of the flask are heated to 200.degree.C. and kept at this
temperature for about 20-22 hours with agitation; approximately 2
ml. of water codistilled over during this time. The reaction
mixture is stripped under reduced pressure and filtered through a
pressure filtration funnel. The Kjeldahl nitrogen determination on
the final oligomeric material gives a value of 0.61% which
corresponds to 0.436 milliequivalents per gram; since the
concentration of the acid is 0.48 milliequivalents per gram, the
reaction yield amounts to 0.436/0.48 .times. 100 = 91%.
* * * * *